Halo active aromatic sulfonamide organic compounds and odor control uses therefor

ABSTRACT

Aromatic N-halosulfonamide organic compounds have been known for over one hundred years. The ability of these compounds to release active halogen ions has been utilized in a range of biocidal and fungicidal applications. The most widely used halogen sulfonamide organic compound for these applications is Chloramine-T. This invention deals with the new use of discovered compositions of matter, halo active aromatic sulfonamide organic compounds and use of solutions of these compounds as, odor control agents. The odor control solutions may be buffered to a predetermined pH. The odor control compositions may further incorporate small percentages of low molecular weight alcohols and wetting agents.

RELATED APPLICATIONS

This application is a continuation of application U.S. patentapplication Ser. No. 11/216,495 filed Aug. 31, 2005, which is acontinuation-in-part of U.S. Pat. No. 7,465,829, filed Feb. 18, 2003,which claims priority to U.S. Provisional Patent Application Ser. No.60/357,265, filed Feb. 19, 2002, each of which is hereby incorporatedherein by reference in its entirety.

BACKGROUND OF THE INVENTION

Halo active aromatic sulfonamide organic compounds have been known forwell over one hundred years. These compounds have been put to a widerange of uses, which include fungicides, biocides, odor control agents,drug reaction intermediates, etc. A widely used sulfonamide organiccompound is Chloramine-T. This invention relates to uses for a new classof halo active aromatic sulfonamide organic compounds which haveenhanced properties and minimal side effects as compared to thecompounds of the prior art. In a broad context this invention relates tothe use of halo active sulfonamide compounds in odor control.

While the new compounds of this invention show improvement in a numberof potential applications such as; biocides, fungicides, odor controlagents, drugs for cultured fish, paint additives, soap additives, stainremovers and treat cleansers, this application is particularly concernedwith odor control.

When the new halo active aromatic sulfonamide compounds of thisinvention are used as a biocide, fungicide, odor control agent, or as atreat cleanser, solutions of the sulfonamide compound are brought intocontact with the surface being treated. This contact is usually affectedby spraying, washing, dipping, and/or mixing in such a manner as tocontact the effected surface or substrate with an aqueous formulation ofthe desired sulfonamide compound or a blended mixture of same.

PRIOR ART

U.S. Pat. No. 6,296,841 discloses the use of Chloramine-T as an odorcontrol agent wherein the Chloramine-T is used with a wetting agent. Thedisclosure relates primarily to domestic odor control.

A related U.S. Pat. No. 6,743,420 B2 discloses the use of Chloramine-Tas an odor control agent wherein the Chloramine-T is used with andwithout a wetting agent. The disclosure of this patent relates todomestic and industrial odor control.

U.S. Pat. No. 6,667,030 BI, further relates to the use of Chloramine T aan odor control agent.

BRIEF DESCRIPTION OF THE INVENTION

This invention relates to odor control. In the prior art odors wereoften masked using perfume type substances or by encapsulating odorousmolecule. This prior art method of odor control does not destroy ormodify the odorous molecule, it only masked the odor. In contrast to theprior art, in accordance with this invention, odors are not controlledby masking or encapsulating but instead odors are controlled by alteringor destroying the odor causing molecule.

Odor control is affected in accordance with this invention by treatingthe odorous substrate with new halo active aromatic sulfonamide organiccompounds. These compounds are effective on a wide range of odoroussubstances as they have the ability to react with odorous molecules, forexample aliphatic, aromatic or heterocyclic oxygen, aliphatic, aromaticor heterocyclic sulfur and/or aliphatic, aromatic or heterocyclicnitrogen containing compounds and/or mixtures thereof, in such a manneras to convert these odorous compounds to a non odorous format.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Halo active aromatic sulfonamide organic compounds have been known andused for over one hundred years. Chloramine-T is an example of an oldsulfonamide organic compound which has been used in many applications.The usefulness of Chloramine-T is predicated on its ability to releasean active Cl+ ion when needed on demand, immediately after which, itsimultaneously generates an active aromatic sulfo nitrene companion ion.The active Cl+ ion starts the conversion process of the odor molecule,it is immediately assisted by the companion aromatic sulfo nitrene whichcompletes the conversion process. This process makes the halo activearomatic sulfonamides useful in the odor control, biocidal andfungicidal arts.

The latent halogen cation ion, prior to release by halo active aromaticsulfonamide organic compounds, in accordance with this invention, isrelativity covalent. This relative covalency assists to prevent the Cl+ion from prematurely reacting and as such prevents the active moleculefrom having detrimental bleaching properties, by remaining bonded untilencountering the odor molecule.

The new halo active aromatic sulfonamide compounds as used in thisinvention have excellent odor control properties. In addition many ofthese compounds have very low toxicity properties which make themattractive for usage, as odor control agents, in human, animal andaquatic environments.

In its broadest sense the subject invention relates to a process forodor control which comprises treating a substrate containing an odoroussubstance, with a solution which has an active aromaticN-halosulfonamide.

While any halo active aromatic sulfonamide is functional in accordancewith this invention, chloro active sulfonamides are preferred.

The new halo active aromatic sulfonamide compounds which contain atleast one halo active sulfonamide group, in accordance with thisinvention, are in accordance with the following Formulas I to IV.

wherein, X is a halogen,

R3 is hydrogen, methyl, or COOM,

R1, R2, R4, R5 are hydrogen, COOH, derivatized COOH, an ester oralkylated amide, COOM, CN, NO₂, SO₃H or derivatized SO₃R, a halogen, asubstituted or unsubstituted phenyl group, a sulfonamide, ahalosulfonamide, a straight or branched aliphatic moiety from C₁ to C₁₂,wherein, the same straight or branched aliphatic moiety may containsubstitution at one or more of the aliphatic hydrogens,

and R1, R2, R4 and R5 are other than all hydrogen,

and M is an alkali or alkaline earth metal.

Additional compounds which are useful in the subject invention are inaccordance with Formula II:

wherein, X is a halogen,

R1, R2, R4, R5 are hydrogen, COOH, derivatized COOH, an ester oralkylated amide, COOM, CN, NO₂, SO₃H or derivatized SO₃R, a halogen, asubstituted or unsubstituted phenyl group, a sulfonamide, ahalosulfonamide, a straight or branched aliphatic moiety from C₁ to C₁₂,wherein, the same straight or branched aliphatic moiety may containsubstitution at one or more of the aliphatic hydrogens.

R3 is an organic derivatized COOH, such as an ester or alkylated amide,CN, NO₂, SO₃H or derivatized SO₃R, a halogen, a substituted orunsubstituted phenyl group, a sulfonamide, a halosulfonamide, a straightor branched aliphatic moiety from C₂ to C₁₂, wherein, the same straightor branched aliphatic moiety may contain substitution at one or more ofthe aliphatic hydrogens,

and M is an alkali or alkaline earth metal.

Other compounds which are useful in this invention as odor controlagents are as per Formula III:

wherein, X is a halogen,

R1, R2, R4, R5 are hydrogen,

R3 is hydrogen, methyl, or COOM,

and M is either potassium, rubidium, cesium, lithium or an alkalineearth metal.

Other compounds which can be used as odor control agents are inaccordance with Formula IV:

wherein, X is bromine, fluorine, or iodine,

R1, R2, R4, R5 are hydrogen,

R3 is hydrogen, methyl, or COOM,

and M is an alkali or alkaline earth metal.

Compounds of Formulas I-IV may or may not be hydrated (n H₂O), but aregenerally isolated as a trihydrate where (n=3).

The compounds of Formulas I-IV are very soluble in water. This propertyallows for easy compounding of odor control compositions and allows highpercentages of the compounds to be formulated into the useful solutionproducts.

Further the compounds of Formulas I-IV have minimal bleach odor. Thisproperty again is highly advantageous, because, formulations with strongbleach odor are undesirable in most applications.

The activity of the aromatic chlorosulfonamido group of the compounds ofFormulas I-IV is regulated by the selection of specific “R” groups. “R”groups adjacent to the chlorosulfonamido group (R₁ and R₅) can causesteric effects and therefore change activity and/or cause stabilitychanges on the chlorosulfonamido group. In addition the various “R”groups can be effected differently. Specific increases or decreases inactivity and, stability may be noted. The usefulness of specificaromatic chlorosulfonamido groups may be affected by their different andunique inductive or resonance effects.

Bleach is commonly used as a source of Cl+ cations which are effectiveas deodorizers. Because of the problems associated with the use ofbleach, i.e. the discoloration of the substrate, and its heavy nondiscrete oxidizing power, it is generally not suitable for use as adeodorizer. In addition the Cl+ cation which is produced by bleach ismuch more ionic and non discrete in its reactions when compared to theCl+ cation produced by the compounds of Formulas I-IV. Further, as thecompounds of Formulas I-IV liberate the Cl+ ion, a companion ion anaromatic sulfo nitrene, is released which also is intimately involved ina reaction to convert the odorous molecule to a non-odorous state. Thatis when compared to the Cl+ cation produced by bleach, the Cl+ cationproduced by the compounds of Formulas I-IV is much more covalent andless ionic and therefore is very selective in its initial reaction as adeodorizer, hence, it will attack the odor source and not the substrate.As a result of this covalence the bleaching side effects resulting fromthe Cl+ cation produced by the compounds of Formulas I-IV do not causethe bleaching problems produced by bleach. Therefore, the Cl+ cationproduced by the compounds of Formulas I-IV can be used to deodorize asthey do not have side effects such as strong bleach smell etc. Generallyit could be said that the compounds of Formulas I-IV are more stablethan bleach and have a higher selectivity as a Cl+ source as compared tothe Cl+ cation produced by bleach. In addition, the N-halogenatedaromatic sulfonamide when activated by an attack on an odorous moleculeby its Cl+, further produces an active aromatic sulfo nitrene which alsomodifies the odor causing molecule in such a manner that it is no longeran odorous molecule.

In summary, compared to bleach the compounds of Formulas I-IV aresuperior deodorizing agents because they are more selective, morecovalent Cl+ and because the backbone companion ion, the aromatic sulfonitrene, remaining after the Cl+ cation is released from the compoundsof Formulas I-IV, is itself very selective but very active andimmediately contributes its odor controlling power. This backbonecompanion ion has the ability to further react with the odor containingmolecule thereby permanently removing it as a potential source of odor.In contrast the chemical moiety which remains after the Cl+ cation isremoved from bleach has no ability to react with odor causing molecules.

Examples of some specific halo active aromatic sulfonamide compoundsthat are useful as odor control agents in accordance with this inventionare as follows:

1. N-chloro-2-tolylsulfonamide sodium salt

having the following Formula:

2. N-chloro-4-chlorobenzenesulfonamide sodium salt

having the following Formula:

3. N-chloro-2-chlorobenzenesulfonamide sodium salt

having the following Formula:

4. N-chloro-4-methoxybenzenesulfonamide sodium salt

having the following Formula:

5. N-chloro-2,4,6-mesitylsulfonamide sodium salt

having the following Formula:

6. N-chloro-4-carboxybenzenesulfonamide dipotassium salt

having the following Formula:

7. N-chloro-4-tolylsulfonamide potassium salt,

having the following Formula:

8. N-chloro-4-fluorobenzenesulfonamide sodium salt,

having the following Formula:

9. N-chloro-4-nitrobenzenesulfonamide sodium salt,

having the following Formula:

The use of wetting agents with various solutions in order to reducesurface tension is common in the prior art. For example wetting agentsare commonly added to herbical solutions to allow the herbicide to wetout plant leaves, likewise the use of wetting agents with insecticidesis common.

Most odor causing molecules are mercaptans, sulfides, nitrogen and/oroxygen based compounds. The compounds of Formulas I-IV are excellentagents for eliminating odors which are mercaptan, sulfides, nitrogenand/or oxygen based compounds since both the Cl+ cation and the aromaticsulfo nitrene made available by the compounds of Formula 1 react withand modify the odor causing molecules to create a chemical moiety whichhas no odor.

In order for the compounds of Formulas I-IV to be effective they mustcome into contact with the substance which is responsible for the odor.If the substance which is responsible for the odor is in an environmentwhich makes access difficult, i.e. pet stains in a carpet, a means mustbe provided for bringing the selected compound of Formulas I-IV intocontact with the odor causing substance. In many instances when aqueoussolution is used as the delivering medium the solution tends to bead upon the substrate. Therefore, when the water component of the solutionevaporates the substance in solution is deposited only in localizedareas. In the case at hand if an aqueous solution of a compound ofFormulas I-IV were applied to a carpet containing a pet stain, thesolution would bead up on the carpet, such that when the waterevaporates the placement the two reactive components of the moleculewould not be such that they could react with the entire odor causingsubstance on a molecular basis. That is the reaction of the odor controlcompound with the pet odor and/or stain would be incomplete, and hencethe odor control would be incomplete.

In accordance with one embodiment of this invention a substance is addedto the solutions of this invention to reduce the surface tension of thesolution. As is discussed above the selected compound of Formulas I-IVfunctions in part by the reaction of the Cl+ moiety with the odorcausing molecule. One aspect of this invention is concerned with thefact that many substances which are suitable for reducing the surfacetension of the solution may adversely affect the formation of the Cl+moiety, from the compounds of Formulas I-IV, or degrade said Cl+ moietyonce it is formed.

Suitable substances which are useful for reducing the surface tension ofthe odor control solutions of this invention are synthetic and naturalwetting agents. Wetting agents are generally classified as cationic,anionic, amphoteric and nonionic. Because there are thousands of naturaland synthetic wetting agents it is impossible to make generalizations asto which wetting agent would be effective in the composition of thisinvention. With this caveat it can be said that generally the mostpreferred wetting agents for use in accordance with odor controlcompositions are anionic wetting agents, with the next preferred classof wetting agents being a nonionic wetting agents.

Amphoteric and cationic wetting agents are least preferred for use withthe wetting agent embodiment of this invention.

Regardless of the above comments satisfactory agents may be found in anyclass of wetting agents.

While the applicant is aware of the vast range of wetting agentsavailable, the applicant is not sure of all ramifications of howdifferent wetting agents degrade the Cl+ moiety. It is felt thatfunctional groups such as alkenes, alcohol, ketone, especially aliphaticketones or aldehydes containing at least one alpha hydrogen next to thecarbonyl carbon, and phenols as may be contained on the base wettingagent molecule are particularly harmful to the Cl+ moiety. Further whileit is impossible for the applicant to explore all the ramificationsthereof, impurities as may be contained in various commerciallyavailable wetting agents can play a significant part in the degradationof the Cl+ moiety. Impurities which are known to facilitate thedegradation of the Cl+ moiety are aromatic and conjugated phenols,compounds containing activated carbonyl, alpha aliphatic hydrogen's oractive primary and secondary amines.

The concentration of the wetting agent used in accordance with the odorcontrol solutions of this invention can be from about 0.1 to 5%. A morepreferred concentration for the wetting agent is from about 0.5 to about1.5%. In order to achieve maximum efficiency in the odor control proceedthe surface tension of the solution must be reduced, so that thecompounds of Formula I can reach and react with the odor causingmolecules.

A factor in choosing the concentration of the wetting agent is thedegree to which it foams. If undesirable foaming occurs anti foamers maybe added to the solution.

For stability and for optimum performance as an odor killing agent thepH of a solution of the compounds of Formulas I-IV should be between6-14, with a more preferred pH range being between 8-9.5 with a mostpreferred range being between 8.5-9.

As is discussed above the pH range for odor control solutions for use inthe invention can be from about 6-14. Below a pH of 6 the compounds ofFormulas I-IV tend to decompose due to the acidic nature of the medium.While the solutions of this invention are effective above a pH of 10.0solutions having a pH of above 10.0 can only be used for industrialapplications, due to their caustic nature.

Aromatic N-Halo active sulfonamide solutions for use in this inventionexhibit excellent stability at a pH range of 8-9.5. This stability isimportant in the domestic applications of this invention where longshelf life is very desirable.

Buffering agents which are suitable for use in accordance with thisinvention are sodium bicarbonate, potassium bicarbonate, sodiumcarbonate, potassium carbonate, acetate buffers (such as sodiumacetate), phosphate buffers (such as tri and di sodium phosphate andmixtures thereof, pH blended phosphates, sulfate buffers (such as di andtri sodium sulfate and mixtures thereof.

Because of price, ease of use, low toxicity and their effect on theenvironment, the above listed sodium and potassium bicarbonates arepreferred buffering agents for use in this invention. Buffered solutionsare advantageous in that the active ingredients of the odor controlsolution of this invention can be shipped in powdered form and mixed bythe consumer with no adverse effect.

The concentration of the buffering agent can be from 0.1% up to thelimit of solubility. The preferred range for the concentration of thebuffering agent is from about 5% to about 200% of the active compound insolution. A more preferred range is from about 5% to about 50% with amost preferred concentration being 25-50%.

The buffering of the solution compensates for any change in pH that mayresult from the conditions of application, the type of substrate, orindustrial waste and the nature of the odor causing molecule.

For the industrial odor control it is preferred that the concentrationof a compound of Formula I be about 5-100%. For residential consumer usethe concentration of the active ingredient can be from about 0.25 toabout 2.0%, with a more preferred range being from about 0.5 to about1.0% percent, with the most preferred concentration being 0.75%. Theselower concentrations keep the bleach like smell to a minimum but stillgive the desired odor control.

As with all household formulations, it is at times desirable to have avery faint but highly attractive scent associated with its application.Therefore, the use of trace amounts of compatible perfume additives maybe used in the formulations of the invention.

Industrial applications for the use of the composition and process ofthis invention relate to controlling odors which are emitted from a widevariety of industrial sludges such as sewerage treatment sludges, papermaking sludges, waste from animal grow outs, animal processing, animalhabitats etc.

Paper mills for example are notorious for creating foul odors. Inparticular the Kraft paper making process produces an odor which isoften categorized as a rotten egg smell. In the past, society wastolerant of these odors as society often took the position that thesmell of a paper mill was the smell of money. The odor of a paper millis primarily based on odorous mercaptans, which the human nose candetect at concentrations which approach one part per billion. Thesepaper mill odors originate from the basic chemistry of the paper makingprocess and can be associated with stack gases, holding ponds which areused to hold the sludge which is a byproduct of the paper makingprocess, and from the sludge which results from the treatment of thepaper mill stack gases or from solid press.

Odors originating with paper mills can often be detected by humans atdistances which can exceed twenty miles. While in the past society wastolerant of these odors in recent times society has become much lesstolerant, therefore it is important that these odors be eliminated.

The process and composition of this invention are particularly suited toeliminating paper mill odors due to the ability of the compounds ofFormulas I-IV to react with odorous mercaptans.

In accordance with the broadest aspects of this invention paper millodors can be effectively controlled using solutions of compounds ofFormulas I-IV.

The preferred solvent is water, however, other solvents can be used. Thesolutions which are used to treat Kraft paper mill stack gases or sludgecan have a concentration of the compounds of Formula I-IV from about 3to about 100 percent with a more preferred range being from about 5 toabout 12 percent with a most preferred concentration being 8 percent.All concentrations are by weight percent.

In treating paper mill sludge is preferred that the solution be bufferedto a pH of about 9.

While a wide variety of buffering agents can be used, the preferredbuffering agents for use in treating paper mill sludge are potassium orsodium bicarbonate.

Further, in accordance with the above discussion, the treating solutionsfor paper mill sludge may incorporate a wetting agent, it is preferredthat the solution incorporate a nonionic wetting agent at aconcentration of from about 0.1 to about 5 weight percent. The caveatsand qualifications for wetting agents as are discussed above likewiseapply for the treatment of paper mill sludge's. The preferred wettingagent for use in conjunction with paper mill sludge treatingcompositions is an anionic wetting agent sold under the trademark AvanelS-74 by the BASF Chemical Co. of Mt. Olive, N.J. The applicant believesthat Avanel S-74 is sulfate capped alkyl ethoxylate, where the wettingagent contains 3 units of ethoxylate and the alkyl is a C8 alkyl.

As is discussed above of the compounds of the general Formulas I-IVfunction as deodorizing agents. The data below demonstrates that thedefined aromatic N-halo sulfonamides will control odor, regardless ofthe specific substation on the structure of Formulas I-IV. This datademonstrates that it is the aromatic N-halo sulfonamide doing the odorcontrol work and the various “R” group combinations will give greater orlesser control of the odor for a given odor problem, however, all of thecompounds of Formula I-IV are functional odor control agents. The N-halosulfonamide is the only common chemical grouping in each of theFormulas. It is safe to say that all aromatic N-halo sulfonamides willshow some activity on all odors and conversely a specific N-halosulfonamide may or may not have the same activity with all odorouscompounds.

It has been found that if the deodorizing compositions of this inventionfurther incorporate small percentages of a low molecular weight alcohol,the activity of the deodorizing compound is enhanced.

An example of a suitable alcohol which is useful in conjunction withthis aspect of the invention is t-butanol. The effect of the alcohol canmanifest itself in many ways. The alcohol enhances the odor removalactivity of the active aromatic N-halo sulfonamide group. The alcoholalso can make the formulation less difficult, the alcohol can addsurface activity, the alcohol can aid in disinfection, the alcohol canenable the use of a more favorable blend of fragrances, surface activecompounds and the like, lastly, the alcohol can help stabilize theformulation, etc. The type of alcohol used however is somewhat limited.T-Butanol or related tertiary alcohols are preferred because they do notcontain hydrogen atoms alpha to the oxygen alcohol moiety, and thereforeoffer a more stable formulations. The alpha hydrogens can detract fromthe stability of the formulations due to interaction with the activehalogen contained in the active aromatic halo sulfonamide. However, atpH>10 alcohols containing alpha hydrogens, such as ethanol andisopropanol, were found to be stable in these odor control formulations.In fact, the halo active sulfonamides are stable at high concentrationsof alcohols (>50%) at pH>10.

The alcohol can be present at concentrations of from about 0.1 to about80 weight percent, a more preferred range is from about 0.1 to about 2.0weight percent with a most preferred range being from about 0.2 to about1.0 weight percent.

While the applicant does not understand all of the ramifications of whycertain alcohols enhance the deodorizing ability of the compounds ofFormulas I-IV, it would appear as though the most functional alcoholsare those with no hydrogens alpha to the oxygen moiety of the alcoholi.e. CH or CH₂ groups next to OH group.

Deodorizing compounds in accordance with this invention can furtherincorporate small percentages of compatible fragrances, i.e. pine,orange, lemon fragrances.

EXAMPLES

The present invention is illustrated by the following Examples which,however, are not to be construed as limiting the invention to theirdetails.

The following Examples illustrate the general utility of N-Halogenatedaromatic sulfonamides in odor control. It has been found that the “R”group substitution has an affect on how effective a given compound is inodor control.

For purposes of conducting the test in accordance with the below listedExamples a series of odorous test reagents were prepared. The utilizedodorous test reagents are in accordance with the following:

Onion:

2 g samples of chopped white onion (Approximately ⅛″ cubes) wereprepared and used for each test.

Garlic:

DMSO (dimethyl sulfoxide) 1 g was used for each test.

Fox Urine:

0.5 g of deer hunter's grade red fox urine was used for each test.

Rotten Egg:

0.1 g of a 5% sodium sulfide solution was added to a beaker and 2 dropsof glacial acetic acid was added to prepare the rotten egg scent andused for each test.

Odor Control Solutions:

Unless otherwise specified separate 1% w/w solutions in water of eachhalo active aromatic sulfonamide derivative were prepared for use. Eachsolution also contained 0.3% Avenal S-74. The pH of the resultingformulations varied between 8.0 and 9.0.

The testing protocol for Examples 1 thru 12 involved is as follows: Thedefined odorous reagents were added to a beaker, watch glass, or petridish. For each aromatic sulfonamide derivative, 3 grams of theformulated odor control solution defined above were sprayed with atrigger sprayer, separately onto each odor (onion, garlic, fox urine,rotten egg. Odor evaluations were then made by a six person human panel.

The evaluation criteria utilized is as follows;

E=Excellent, immediate removal of odor, no remaining odor.

G=Good, Immediate (within seconds) reduction of odor, very slight butdetectable trace odor remains.

F=Fair, Immediate (within seconds) reduction, more pronounced odorremains.

P=Detectable reduction in odor but rate of reduction is slow and a muchmore pronounced odor remains.

All test evaluations were made at 20° C.

Example 1

The structure of halo aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg G P G E

Example 2

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E G E E

Example 3

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E F G E

Example 4

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E P G E

Example 5

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E P E E

Example 6

The structure of halo aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E G E E

Example 7

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg P P P P

Example 8

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E P F E

Example 9

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E G E E

Example 10

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E G E E

Example 11

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg G F E F

Example 12

The structure of halo active aromatic sulfonamide compound tested is asfollows:

Test odors were prepared and odor evaluation conducted, the resultingtest results are as follows:

Onion Garlic Fox Urine Rotten Egg E F E E

Example 13

Industrial waste water odor. A 100 g sample of an industrial waste waterhaving a strong sulfur type odors were placed in a beaker and treatedwith 1.0 g of the following formulation.

Formulation w/w % N-chloro-4-tolylsulfonamide sodium salt, akaChloramine-T   8% Avenal S-74 0.3% Sodium Bicarbonate   2% Water 89.7% Ph 8.5

An evaluation by a panel of six humans determined that all odor waseliminated.

Example 14

Skunk oil was applied to a 5×5 swatch of nylon pile carpet. The sampleshad a very noticeable skunk odor. The swatch was treated with 3 pulls ofa trigger spray (Approx 2.6 g of the formulation). The odor of theswatch immediately changed from an overbearing skunk odor to no skunkodor using a 6 human panel test.

The Formulation utilized was: w/w % 4-tolylsulfonamide sodium salt, akaChloramine-T 0.8% Avenal S-74 0.03%  Sodium Bicarbonate 0.2% Water  99%

Example 15

Garbage disposal odor removal. A used garbage disposal which was foundto have residual unpleasant odor after water was continuously runthrough the disposal for 3 minutes. The garbage disposal was treatedwith 5 trigger pulls (approximately 4.3 g) of the following solution:

Formulation w/w % N-chloro-4-carboxybenzenesulfonamide disodium salt  1% Avenal S-74 0.03%  Sodium Bicarbonate 0.2% Fragrance 0.1% Water98.7% 

A 6 person panel evaluated the odor immediately after application of thesolution and found no objectionable odor remained. Water was run throughthe disposal for approximately 3 minutes and the odor was againevaluated by the panel which found no unpleasant odor.

Example 16

Industrial waste sludge odor. A 100 g sample of industrial waste sludge(solids and aqueous compounds) containing very strong sulfur type odorswas placed in a beaker and treated with 2.0 g of the followingformulation. The solution was stirred for 1 minute. The formulationutilized is as follows.

Formulation w/w % N-chloro-4-carboxybenzenesulfonamide disodium salt 10% Avenal S-74 0.3% Sodium Bicarbonate   2% Water 87.7% 

A six person human panel found that all unpleasant odors wereeliminated.

Example 17

Dog odor. A used dog bed (approx 30″ diameter) containing disagreeableodor was sprayed with 10 trigger pulls (approx. 8.5 g) of theformulation. A 6 person panel determined that all disagreeable odor wasimmediately eliminated.

The formulation utilized is as follows.

Formulation w/w % N-chloro-4-carboxybenzenesulfonamide disodium salt0.6% N-chloro-4-tolylsulfonamide sodium salt, aka Chloramine-T 0.3%Avenal S-74 0.03%  Sodium Bicarbonate 0.2% t-Butanol 0.5% Fragrance 0.1%Water 98.3% 

Example 18

Cat odor. Used cat litter boxes (approx. 20″×16″) all of which had anunpleasant odor were sprayed with 5 trigger pulls (approx. 4.3 g) of theformulation. The litter boxes were evaluated by a panel of 6 humans,after treatment the panel found that the unpleasant odors wereeliminated.

The formulation utilized is as follows:

Formulation w/w % N-chloro-4-carboxybenzenesulfonamide disodium salt0.6% N-chloro-4-tolylsulfonamide sodium salt, aka Chloramine-T 0.15% Avenal S-74 0.03%  Sodium Bicarbonate 0.2% t-Butanol 0.5% Fragrance 0.1%Water 98.4% 

Example 19

To a 5×5 swatch of nylon pile carpet 1 g of fox urine was applied. Theswatch was treated with 3 pulls of a trigger spray (approx. 2.6 g of theformulation was sprayed on to the swatch). The odor of the swatch wasimmediately evaluated by a 6 person panel and found no trace of urineodor.

The formulation utilized is as follows:

Formulation w/w % N-chloro-4-carboxybenzenesulfonamide disodium salt0.6% N-chloro-4-tolylsulfonamide sodium salt, aka Chloramine-T 0.3%Avenal S-74 0.03%  Sodium Bicarbonate 0.2% t-Butanol   2% Water 96.9% 

Example 20

In order to evaluate the stability of various sulfonamide compounds foruse in odor control, the stability ofN-chloro-4carboxybenzenesulfonamide disodium salt was evaluated atvarious pHs. A base sulfonamide formulation was prepared in accordancewith the following formulation:

Formulation w/w % N-chloro-4-carboxybenzenesulfonamide disodium salt  1% Avenal S-74 0.03% Sodium Bicarbonate  0.2% t-Butanol   1% Water97.8%

The pH of 20 ml sample of the base formulation is 8.7. The temperatureof the sample was raised to 50° C. and the sample was allowed to standfor 30 days. At the end of this period it was found that 99.5% of theN-chloro-4-carboxybenzene sulfonamide disodium salt remained.

21. The test protocol of Example 20 was repeated except that the pH ofthe sample was adjusted to 6.0, with 1N sulfuric acid and the sample wasallowed to stand for 1 day. At the end of this period 0%, of theN-chloro-4-carboxybenzenesulfonamide disodium salt remained.

22. The test procedure of Example 20 was repeated, wherein the pH of thesample was adjusted to 6.0 with 1N sulfuric acid and the t-Butanol wasreplaced with ethanol. The solution was allowed to stand 1 day at whichtime 0% of the sulfonamide compound remained.

23. The test procedure of Example 20 was repeated where the pH of thesample was 8.7 and the t-butanol was replaced with ethanol. The samplewas allowed to stand for 7 days. At the end of this period 0%, theN-chloro-4-carboxybenzenesulfonamide disodium salt remained.

24. The test procedure of Example 20 was repeated, wherein the pH of thesample was adjusted to 10.3 with 1N sodium hydroxide and the t-Butanolwas replaced with ethanol. The solution was allowed to stand 30 days atwhich time 70% of the sulfonamide compound remained.

25. The test procedure of Example 20 was repeated, wherein the pH of thesample was adjusted to 6.0 with 1N sulfuric acid and the t-Butanol wasreplaced with isopropanol. The solution was allowed to stand 1 day atwhich time 0% of the sulfonamide compound remained.

26. The test procedure of Example 20 was repeated where the pH of thesample was 8.7 and the t-butanol was replaced with isopropanol. Thesample was allowed to stand for 7 days. At the end of this period 50%,the N-chloro-4-carboxybenzenesulfonamide disodium salt remained.

27. The test procedure of Example 20 was repeated, wherein the pH of thesample was adjusted to 10.3 with 1N sodium hydroxide and the t-Butanolwas replaced with isopropanol. The solution was allowed to stand 30 daysat which time 90% of the sulfonamide compound remained.

Discussion of the Examples

Examples 1 to 27 demonstrate that sulfonamide compounds when used inaccordance with this invention exhibit substantial odor controlproperties. As can be seen from the data of the Examples in allinstances the various odors were mitigated to an acceptable level.

Further, the data of Examples 13 to 27 demonstrate the effect of pH onvarious sulfonamide formulations and the effect of the addition ofvarious low molecular weight alcohols to the formulations.

1. A process for controlling odor being emitted by an odor causingmaterial which comprises treating the material with a solutioncontaining an effective amount of a halo active aromatic sulfonamidecompound having the formula:

wherein X is a halogen; R₃ is hydrogen, methyl, or COOM; R₁, R₂, R₄, andR₅ are independently selected from hydrogen, COOH, an ester or alkylatedamide, COOM, CN, NO₂, SO₃H, a halogen, a substituted or unsubstitutedphenyl group, a sulfonamide, a halosulfonamide, or a straight orbranched aliphatic C₁₋₁₂ moiety which may be substituted; R₁, R₂, R₄ andR₅ are other than all hydrogen; and M is an alkali or alkaline earthmetal.
 2. The process of claim 1 wherein the solution furtherincorporates an effective amount of a wetting agent which essentiallydoes not react with the sulfonamide compound.
 3. The process of claim 2wherein the wetting agent is an anionic or nonionic wetting agent. 4.The process of claim 1 wherein the solution is buffered to a pH of fromabout 7 to about
 10. 5. The process of claim 1 wherein the solution isbuffered to a pH of from about 8 to about 9.5.
 6. The process of claim 1wherein the solution is buffered with sodium bicarbonate to a pH of fromabout 8.5 to about
 9. 7. The process of claim 1 wherein the pH of thesolution is buffered to a pH of greater than
 10. 8. The process of claim1 wherein the concentration of the sulfonamide compound is from about0.5 to about 10 weight percent.
 9. The process of claim 1 wherein thesulfonamide compound has the following Formula:


10. The process of claim 1 wherein the solution further incorporates aneffective amount of a low molecular weight alcohol.
 11. A process forcontrolling odor being emitted by an odor causing material whichcomprises treating the material with a solution containing an effectiveamount of a halo active aromatic sulfonamide compound having theformula:

wherein X is a halogen; R₁, R₂, R₄, and R₅ are independently hydrogen,COOH, an ester or alkylated amide, COOM, CN, NO₂, SO₃H, a halogen, asubstituted or unsubstituted phenyl group, a sulfonamide, ahalosulfonamide, or a straight or branched C₁₋₁₂ aliphatic moiety whichmay be substituted; R₃ is halogen; and M is an alkali or alkaline earthmetal.
 12. The process of claim 11 wherein the sulfonamide compound hasthe following Formula:


13. The process of claim 11 wherein the sulfonamide compound has thefollowing Formula: